Acta Cryst. (2010). E66, m1500 [ doi:10.1107/S1600536810043977 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-N,N-dimethyldithiocarbamato-![[kappa]](/logos/entities/kappa_rmgif.gif)
3S,S':S)]In the title compound, [Cd(C3H6NS2)2]n, the CdII atom, lying on a twofold rotation axis, is coordinated by six S atoms from four different N,N-dimethyldithiocarbamate ligands in a distorted octahedral geometry. The bridging of S atoms of the ligands leads to the formation of a one-dimensional structure along [001].
A mixture containing 0.005 mmol of Cd(NO3)2.4H2O and 0.010 mmol of dimethyldithiocarbamic acid was placed in a small vial containing MeOH (3.0 ml), DMF (1.0 ml) and H2O (0.5 ml). The vial was sealed, heated at 373 K for 2 d and allowed to cool to room temperature. Colorless crystals suitable for X-ray diffraction were collected and dried in air (yield: 50%).
H atoms were placed in calculated positions and treated using a riding model, with C—H = 0.98 Å and with Uiso(H) = 1.5Ueq(C).
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./hy2367fig1thm.gif)
| Fig. 1. The asymmetric unit of the title compound, showing the Cd coordination. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 3/2-x, y, 1/2+z; (ii) 3/2-x, 1/2-y, z; (iii) x, 1/2-y, 1/2+z.] |
![[Figure 2]](./hy2367fig2thm.gif)
| Fig. 2. One-dimensional chain in the title complex. H atoms have been omitted for clarity. |
| [Cd(C3H6NS2)2] | F(000) = 696 |
| Mr = 352.82 | Dx = 1.988 Mg m−3 |
| Orthorhombic, Pccn | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ab 2ac | Cell parameters from 4468 reflections |
| a = 10.055 (2) Å | θ = 2.5–27.6° |
| b = 14.744 (3) Å | µ = 2.52 mm−1 |
| c = 7.9518 (17) Å | T = 296 K |
| V = 1178.9 (4) Å3 | Block, colorless |
| Z = 4 | 0.54 × 0.22 × 0.17 mm |
| Bruker APEXII CCD diffractometer | 1370 independent reflections |
| Radiation source: fine-focus sealed tube | 1221 reflections with I > 2σ(I) |
| graphite | Rint = 0.030 |
| φ and ω scans | θmax = 27.6°, θmin = 2.5° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
| Tmin = 0.519, Tmax = 0.652 | k = −16→19 |
| 9543 measured reflections | l = −10→10 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.017 | H-atom parameters constrained |
| wR(F2) = 0.044 | w = 1/[σ2(Fo2) + (0.0174P)2 + 0.6307P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max = 0.001 |
| 1370 reflections | Δρmax = 0.29 e Å−3 |
| 63 parameters | Δρmin = −0.33 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0036 (3) |
| [Cd(C3H6NS2)2] | V = 1178.9 (4) Å3 |
| Mr = 352.82 | Z = 4 |
| Orthorhombic, Pccn | Mo Kα radiation |
| a = 10.055 (2) Å | µ = 2.52 mm−1 |
| b = 14.744 (3) Å | T = 296 K |
| c = 7.9518 (17) Å | 0.54 × 0.22 × 0.17 mm |
| Bruker APEXII CCD diffractometer | 1370 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1221 reflections with I > 2σ(I) |
| Tmin = 0.519, Tmax = 0.652 | Rint = 0.030 |
| 9543 measured reflections | θmax = 27.6° |
| R[F2 > 2σ(F2)] = 0.017 | H-atom parameters constrained |
| wR(F2) = 0.044 | Δρmax = 0.29 e Å−3 |
| S = 1.07 | Δρmin = −0.33 e Å−3 |
| 1370 reflections | Absolute structure: ? |
| 63 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| Cd1 | 0.7500 | 0.2500 | 0.17288 (2) | 0.03178 (9) | |
| S1 | 0.49818 (5) | 0.28596 (4) | 0.11658 (7) | 0.04016 (14) | |
| S2 | 0.71139 (5) | 0.37665 (3) | −0.08336 (6) | 0.03093 (12) | |
| N1 | 0.45119 (16) | 0.39753 (11) | −0.1396 (2) | 0.0335 (4) | |
| C1 | 0.54274 (18) | 0.35704 (12) | −0.0449 (2) | 0.0279 (4) | |
| C2 | 0.3088 (2) | 0.38157 (18) | −0.1150 (3) | 0.0473 (5) | |
| H2A | 0.2952 | 0.3465 | −0.0118 | 0.071* | |
| H2B | 0.2734 | 0.3477 | −0.2112 | 0.071* | |
| H2C | 0.2626 | 0.4399 | −0.1057 | 0.071* | |
| C3 | 0.4855 (2) | 0.45777 (16) | −0.2802 (3) | 0.0481 (5) | |
| H3A | 0.5549 | 0.5003 | −0.2446 | 0.072* | |
| H3B | 0.4063 | 0.4917 | −0.3151 | 0.072* | |
| H3C | 0.5181 | 0.4215 | −0.3749 | 0.072* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cd1 | 0.02789 (12) | 0.04207 (14) | 0.02537 (12) | 0.00462 (8) | 0.000 | 0.000 |
| S1 | 0.0295 (2) | 0.0507 (3) | 0.0403 (3) | 0.0030 (2) | 0.0035 (2) | 0.0156 (2) |
| S2 | 0.0294 (2) | 0.0340 (2) | 0.0294 (2) | −0.00350 (18) | −0.00062 (18) | −0.00097 (18) |
| N1 | 0.0323 (8) | 0.0348 (9) | 0.0333 (8) | 0.0051 (7) | −0.0036 (7) | 0.0015 (7) |
| C1 | 0.0298 (9) | 0.0284 (9) | 0.0256 (9) | 0.0017 (7) | −0.0001 (7) | −0.0039 (7) |
| C2 | 0.0331 (11) | 0.0580 (14) | 0.0509 (13) | 0.0091 (10) | −0.0074 (10) | 0.0033 (11) |
| C3 | 0.0544 (13) | 0.0434 (12) | 0.0466 (12) | 0.0058 (10) | −0.0070 (11) | 0.0154 (10) |
| Cd1—S1 | 2.6255 (7) | N1—C3 | 1.469 (3) |
| Cd1—S2 | 2.7909 (6) | C2—H2A | 0.9800 |
| Cd1—S2i | 2.7194 (6) | C2—H2B | 0.9800 |
| S1—C1 | 1.7169 (19) | C2—H2C | 0.9800 |
| S2—C1 | 1.7473 (19) | C3—H3A | 0.9800 |
| S2—Cd1ii | 2.7194 (6) | C3—H3B | 0.9800 |
| N1—C1 | 1.331 (2) | C3—H3C | 0.9800 |
| N1—C2 | 1.464 (3) | ||
| S1—Cd1—S1iii | 160.37 (3) | C1—N1—C2 | 121.94 (18) |
| S1—Cd1—S2i | 96.922 (18) | C1—N1—C3 | 122.66 (17) |
| S1iii—Cd1—S2i | 97.039 (16) | C2—N1—C3 | 115.34 (17) |
| S1—Cd1—S2iv | 97.039 (16) | N1—C1—S1 | 121.09 (14) |
| S1iii—Cd1—S2iv | 96.922 (18) | N1—C1—S2 | 119.88 (14) |
| S2i—Cd1—S2iv | 89.07 (3) | S1—C1—S2 | 119.03 (10) |
| S1—Cd1—S2iii | 98.326 (18) | N1—C2—H2A | 109.5 |
| S1iii—Cd1—S2iii | 66.812 (15) | N1—C2—H2B | 109.5 |
| S2i—Cd1—S2iii | 163.74 (2) | H2A—C2—H2B | 109.5 |
| S2iv—Cd1—S2iii | 94.63 (2) | N1—C2—H2C | 109.5 |
| S1—Cd1—S2 | 66.812 (15) | H2A—C2—H2C | 109.5 |
| S1iii—Cd1—S2 | 98.326 (18) | H2B—C2—H2C | 109.5 |
| S2i—Cd1—S2 | 94.63 (2) | N1—C3—H3A | 109.5 |
| S2iv—Cd1—S2 | 163.74 (2) | N1—C3—H3B | 109.5 |
| S2iii—Cd1—S2 | 86.22 (3) | H3A—C3—H3B | 109.5 |
| C1—S1—Cd1 | 89.95 (6) | N1—C3—H3C | 109.5 |
| C1—S2—Cd1ii | 98.61 (6) | H3A—C3—H3C | 109.5 |
| C1—S2—Cd1 | 84.06 (6) | H3B—C3—H3C | 109.5 |
| Cd1ii—S2—Cd1 | 92.35 (2) |
| Symmetry codes: (i) −x+3/2, y, z+1/2; (ii) −x+3/2, y, z−1/2; (iii) −x+3/2, −y+1/2, z; (iv) x, −y+1/2, z+1/2. |
| Cd1—S1 | 2.6255 (7) | Cd1—S2i | 2.7194 (6) |
| Cd1—S2 | 2.7909 (6) |
| Symmetry codes: (i) −x+3/2, y, z+1/2. |
This work was supported by the Ningbo Natural Science Foundation (grant No. 2010 A610060), the `Qianjiang Talent' Projects of Zhejiang Province (grant No. 2009R10032), the Program for Innovative Research Team of Ningbo Novel Photoelectric Materials and Devices (grant No. 2009B21007), and the K. C. Wong Magna Fund of Ningbo University.
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Rapid development of metal–organic frameworks has been made in recent years not only for their potential applications in materials science but also for fascinating architectures and topologies (Kitagawa et al., 2006; Papaefstathiou & MacGillivray, 2003; Yaghi et al., 1998). Dimethyldithiocarbamic acid is widely used in latex industry. Its natrium, zinc and copper salts are applied widely in antimicrobial, antisepsis and accelerant (Einstein & Field, 1974; Oskarsson & Ymén, 1983). Meanwhile, dimethyldithiocarbamic acid, possessing two S atoms, is a good candidate to coordinate metal atoms and generates rich hydrogen bonding modes. Herein we report the preparation and characterization of the first cadmium complex of dimethyldithiocarbamic acid.
In the title complex, the CdII ion is coordinated in an octahedral geometry by six S atoms from four different dimethyldithiocarbamate ligands (Fig. 1), with the Cd—S distances ranging from 2.6255 (7) to 2.7909 (6) Å (Table 1). Through the bridging of S2 atoms, the title complex forms a one-dimensional structure (Fig. 2).